CN1133413C - Alpha-hydroxy fatty acid derivatives and composition for external use containing same - Google Patents

Alpha-hydroxy fatty acid derivatives and composition for external use containing same Download PDF

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CN1133413C
CN1133413C CNB998066419A CN99806641A CN1133413C CN 1133413 C CN1133413 C CN 1133413C CN B998066419 A CNB998066419 A CN B998066419A CN 99806641 A CN99806641 A CN 99806641A CN 1133413 C CN1133413 C CN 1133413C
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fatty acid
alpha
acid
hydroxy fatty
alkyl
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CN1303260A (en
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药丸雅史
弘子
中津川弘子
子
岩本美子
池本毅
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Kao Corp
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61Q19/00—Preparations for care of the skin
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
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    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair

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Abstract

A novel oily base which has excellent stability and a low melting point, does not irritate the skin, and gives an excellent use feeling; and a composition for external use. The base comprises one or more alpha -hydroxy fatty acid derivatives represented by general formula (1), and the composition contains at least one of the derivatives wherein R<1> is linear or branched C<10-24> alkyl; R2 is linear or branched C<1-31> alkyl, and R<3> is linear or branched C<11-31> alkyl.

Description

Alpha-hydroxy fatty acid derivant and contain the topical composition of the used for cosmetic of this derivant
Technical field
The present invention relates to a kind of new alpha-hydroxy fatty acid derivant reaches to contain the topical composition that this derivant is the used for cosmetic of feature.
Background technology
For making the moisture loss of inhibition from skin or hair, and the purpose of paying its slickness and glossiness etc. is used the oleaginous base agent usually.These oleaginous base agent are because it uses position is the skin or the hair of human body, so the matrix agent of its composition and the similar human body component of character is ideal, particularly see that from the angle of safety for nonirritant such as skin and toxicity be important.
So far, once studied the sebum institute similar compounds that relates to the people, once attempted in recent years in addition being used in people's the horny layer and contain many ceramides (ceramide) (special open 6-57651 communique, special fair 6-37429 communique).In addition, be ideal owing to have near the chemical compound of fusing point surface temperature of body temperature or skin or below it, so, once attempted in the structure of chemical compound, importing unsaturated bond in order to obtain having the chemical compound of such fusing point.But, usually the phat fat that has unsaturated bond is very unstable for light or air etc., except that oxidized easily shortcoming is arranged, its oxide goes out very strong zest or toxicity for cutaneous manifestations, so must take the anti-oxidation processing of Denging when such phat fat is fitted in skin preparations for extenal use.On the other hand, ceramide costliness, the fusing point that is contained at people's horny layer is generally all very high mostly, and tangible crystallinity is arranged, so its purposes is very limited.On the other hand, report was once arranged as having (T.Nikkari andE.Haahti by the paraffin diester that alpha-hydroxy fatty acid and fatty acid and higher alcohol constituted on the surface of the hair of animals such as cattle, sheep, cat at nature, Biochim.Biophys.Acta, 164,294-305) (1968) N.Nicolaides, H.C.Fu and M.N.A.Ausari, Lipids, 5,299-307 (1970).These paraffin diester, wherein Alpha-hydroxy fat is with carbon number 14-22, and fatty acid is with carbon number 14-28, and higher alcohol as the chemical compound that main component was constituted, is the chemical compound that short-chain fatty acid constituted of 2-6 etc. by carbon number and there is not report with carbon number 14-28.In addition, do not see as yet any report of the paraffin diester with this spline structure as topical composition.
Summary of the invention
The topical composition that the purpose of this invention is to provide a kind of new oiliness matrix agent and used for cosmetic.Its excellent in stability of this matrix agent, fusing point be low, non-stimulated and usability is good to skin.
Present inventors have carried out research with keen determination to achieve these goals, found that, with the alpha-hydroxy fatty acid derivant shown in the following general formula (1).Though this derivant is a saturated compounds, have fusing point low, to skin nonirritant and usability also good etc. with the corresponding to characteristic of the object of the invention, and then finished the present invention.That is to say that the present invention is the topical composition that contains a kind of or used for cosmetic more than 2 kinds of the alpha-hydroxy fatty acid derivant shown in the useful following general formula (1).
In the formula, R 1Be the alkyl of the straight or branched of carbon number 10-24, R 2Be the alkyl of the straight or branched of carbon number 1-31, R 3Alkyl for the straight or branched of carbon number 11-31.
In addition, the present invention is for the alpha-hydroxy fatty acid derivant shown in the following general formula of a kind of usefulness (2) and to contain the topical composition that this derivant is the used for cosmetic of feature.
Figure C9980664100052
In the formula, R 4Alkyl, R for the straight chain of carbon number 10-20 5Be the straight chain of carbon number 1-5 or alkyl, the R of abnormal shape or anteiso-type side chain 6Be the straight chain of carbon number 11-31 or the alkyl of abnormal shape or anteiso-type side chain.
Description of drawings
Fig. 1 is an expression 2-palmityl azyloxy Palmic acid palmityl ester of the present invention (2-palmitoyloxypalmitic acid pal mityl ester) 13The spectrogram of R-NMR.
Fig. 2 is expression 2-isobutyl acyloxy long-chain fatty acid of the present invention (14-25) long-chain branched-chain alcoho (12-31) ester 13The R-NMR spectrogram.
Fig. 3 is the expression paraffin diester fraction by down goat of the present invention (alpha-hydroxy fatty acid derivant mixture) 13The spectrogram of R-NMR.
Fig. 4 is the gas chromatogram spectrogram of expression by the resulting alpha-hydroxy fatty acid of alpha-hydroxy fatty acid derivant mixture of down goat.
Fig. 5 is the gas chromatogram spectrogram by the resulting fatty acid of alpha-hydroxy esters pipecolic acid derivative mixture of down goat of expression.
Fig. 6 is the gas chromatogram spectrogram of expression by the resulting alcohol of alpha-hydroxy esters pipecolic acid derivative mixture of down goat.
The specific embodiment
Explain embodiments of the invention below.
The alpha-hydroxy esters pipecolic acid derivative of described general formula of the present invention (1) and general formula (2), can be being that raw material uses with the alpha-hydroxy esters pipecolic acid derivative of the represented alpha-hydroxy fatty acid of following chemical formula (3) or this fatty acid methyl ester etc., with the derivative of fatty acid of the represented fatty acid of following chemical formula (4) or this fatty acid anhydride, oxyhalide etc., with the represented higher alcohol of following chemical formula (5), and can make with known method.
In the formula, R 7Alkyl for the straight or branched of carbon number 10-24.
Figure C9980664100062
In the formula, R 8Alkyl for the straight or branched of carbon number 1-31.
R 9-CH 2-OH (5)
In the formula, R 9Alkyl for the straight or branched of carbon number 11-31.
That is to say, use known acidic catalyst or yeast etc. easily to make.And, can carry out deoxidation, decolour and take off refinement treatment such as flavor as required with conventional method.In addition, though alpha-hydroxy fatty acid mono alkyl ester that unreacted alpha-hydroxy fatty acid, fatty acid, higher alcohol and intermediate product are arranged etc. remaining sneak into also passable.
In addition, alpha-hydroxy fatty acid derivant of the present invention (1) and (2) are by extracting from the hair of down goat with organic solvent etc.And also available as required conventional method is made with extra care.In addition, in alpha-hydroxy fatty acid derivant (2), do not exist, and be the material that is contained in this derivant (1) at the surperficial existing material of the hairs of animals such as cattle, sheep, cat.
By resulting alpha-hydroxy fatty acid derivants of the present invention such as said methods, because low, safety of its fusing point and usability etc., can be used for cooperating skin compositions such as washing liquid, emulsion, cream, beauty and make-up category, facial cleanser, substrate class, lipstick class, bath lotion, shampoo, Hair setting liquid, suppurative mastitis wet goods hair grooming compositions.That is, can be used for preparing common cosmetics, external medicine, medicine etc.
In addition, in topical composition of the present invention, the use level of alpha-hydroxy fatty acid derivant according to utilizing factors such as cooperating resulting effect and cost, is that 0.1-60.0 weight % (to call wt% in the following text) is ideal for total topical composition.
In topical composition of the present invention, can be used on the common compositions that cooperate such as cosmetics, topical drug, medicine as required.Just, as concrete composition, can enumerate oils, colorant, spice, antiseptic, surfactant, pigment, antioxidant, chelating agen, UV absorbent, ultraviolet scattering diluent, macromolecule adhesive, inorganic salts, polyhydric alcohol, vitamins, higher alcohol, vegetable oil extract etc.In addition, so-called in this manual topical composition also comprises hair grooming compositions and skin composition.
As surfactant, can be in order to any in cation, anion, nonionic, both sexes and other the surfactant.As cationic surfactant, can enumerate aliphatic amine salt, quaternary ammonium salt, alkyl three alkylene base ethylene glycol ammonium salts, alkane ether ammonium salt, pyridiniujm or ring type quaternary ammonium salts such as imidazoline salt, bromo geramine salt.Can enumerate the carboxylate of acyl amino hydrochlorate, alkane ether hydroxyl carboxylate, soap etc. as anion surfactant; The sulfonate of N-acyl methyl taurine salt, alpha-alkene sulfonate etc.; The sulfate of alkyl sulfate, fatty acid alkanol amides sulfate etc.; The phosphate of polyoxyethylene alkyl ether phosphate, fatty acid amide ether phosphate etc.Can enumerate polyol fatty acid ester or polyol alkyl ethers such as Sorbitol fatty acid ester, sucrose fatty acid ester, ethylene glycol fatty acid ester as non-ionic surface active agent; The polyoxyethylene ether of polyoxyethylene groups alkyl ether, polyxyethylated phenylate, polyoxyethylene cholesterol, polyoxyethylene polyoxy-propylene etc.; The ether-ether of polyoxyethylene mono fatty acid ester, Polyethylene Glycol di fatty acid ester, Polyoxyethylene Sorbitol Fatty Acid Esters, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkyl ether fatty acid ester, Glucam E-10 fatty acid ester etc.; The nitrogen containing derivative of alkyl amine oxide, polyoxyethylene alkyl amine, alkyl diglycollic amide etc.Can enumerate the carboxylic acid type of glycine type, alanine type, carboxybetaine type, sulfonic acid type, sulfuric acid type, phosphatic type, sulfobetaines type etc. as amphoteric surfactant.Surfactant as other can be enumerated silicone-based such as fluorine system, polyether modified silicone, amino modified silicone, saponarin, natural surfactants such as lecithin.
Can enumerate ethylene glycol, diethylene glycol, triethylene glycol, Polyethylene Glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerol, two glycerol, polyglycerol, 3-methyl isophthalic acid, 3-butanediol, 1,3 butylene glycol, saccharide as polyhydric alcohol.
As higher alcohol, but indistinction ground uses natural or synthetic higher alcohol, can be straight chain, side chain, saturated or undersaturated any.Can enumerate isooctadecane alcohol, octyldodecanol, hexyl decane alcohol, dodecanol, tetradecanol, octadecanol, oleyl alcohol, tadenan, hexadecanol etc. particularly.
Give more detailed description below by embodiment to the present invention, but the invention is not restricted to these embodiment.
The manufacturing of embodiment 1. 2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi esters
After in 2-hydroxy-palmitic acid 27.2g, spermol 24.2g, adding normal hexane 100ml and heating for dissolving, adding is fixed on the heat-resisting lipase of neutrality mixture 4g (the fixed fat enzyme of acrylic resin, Novozym 435, Novo Nordisk A/S society system), remove the water that is generated at 60 ℃ and reacted simultaneously 6 hours.Then,, remove the fixed fat enzyme, under reduced pressure obtain flaxen paraffin except that desolvating by filtering.
(launch solvent: hexane/ethyl acetate=10/1) refining this paraffin, (launch solvent: fraction hexane/ethyl acetate=10/1) obtains the white solid of 38.5g to the Rf value of analyzing by concentrated TLC 0.57 with silica gel column chromatography.At this white solid 13During R-NMR measures from observe 175.5,70.5, the signal of 65.7ppm, can confirm to generate 2-hydroxy-palmitic acid Petiolus Trachycarpi ester.
Be used in made 2-hydroxy-palmitic acid Petiolus Trachycarpi ester 25.7g of said method and Palmic acid chloride 13.7g, in the presence of pyridine, react according to a conventional method.After reaction finishes, add chloroform, under acid condition, wash then, under reduced pressure remove and desolvate, obtain flaxen paraffin.(launch solvent: hexane/ethyl acetate=20/1) make with extra care, (launch solvent: fraction hexane/ethyl acetate=10/1) obtains the 34g white solid by concentrating lamellae Rf value 0.86 with silica gel column chromatography with this paraffin.At this white solid 13During R-NMR measures, as shown in Figure 1, from observe 173.3,170.6,72.3, the signal of 65.3ppm, can confirm to generate the 2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi ester of alpha-hydroxy fatty acid derivant of the present invention.In addition, 13C-NMR measures as determinator and uses JNM-LA 400 (400MHz) (NEC society system), uses heavy chloroform (CDCl as measuring solvent 3), use TMS to carry out as demarcating material.Below, 13C-NMR measures and carries out with identical method.
The manufacturing of embodiment 2. 2-isobutyl acyloxy tetradecylic acid-(18)-methyl 20 esters.
In 2-hydroxy tetradecanoic acid methyl ester 26.1g, 18-methyl eicosanol 31g, add n-hexane 200ml and heating for dissolving, add fixed fat enzyme (Novozym IM then, Novo Nordisk A/S society system) 3g removes the methanol that is generated on 60 ℃ of limits and reacted simultaneously 5 hours.Then,, use the method identical to make with extra care, obtain white solid 37.6g with embodiment 1 by removing by filter the fixed fat enzyme.At this white solid 13During R-NMR measures from observe 175.5,70.5, the signal of 65.7ppm can confirm to generate 2-hydroxy tetradecanoic acid-(18)-methyl 20 esters.
Be used in 2-hydroxy tetradecanoic acid-(the 18)-methyl 20 ester 26.3g and the isopropylformic acid. chloride 6.0g of said method manufacturing, make and refining, obtain white solid 26.5g by the method identical with embodiment 1.At this white solid 13During C-NMR measures from observe 176.5,170.6,72.2, the signal of 65.3ppm, can confirm to be generated as 2-isobutyl acyloxy 14-(18)-methyl 20 esters of alpha-hydroxy fatty acid derivant of the present invention.
The manufacturing of embodiment 3. 2-acetoxyl group stearic acid-(18)-methyl 19 esters
Remove and change 2-hydroxy tetradecanoic acid methyl ester into the 2-hydroxystearic acid methyl ester, 18-methyl eicosane changes 18-methyl nonadecane into, the isopropylformic acid. chloride changes into beyond the acetic acid chloride, makes 2-acetoxyl group stearic acid-(18)-methyl 19 esters with manufacture method similarly to Example 2.What measure with the white solid of above-mentioned manufacture method gained 13Among the R-NMR, from observe 170.46,170.44,72.5, the signal of 65.3ppm, can confirm to be generated as 2-acetoxyl group stearic acid-(18)-methyl 19 esters of alpha-hydroxy fatty acid derivant of the present invention.
The manufacturing of embodiment 4. 2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) esters
Except that replacing the 2-hydroxy-palmitic acid with the product that according to a conventional method long-chain alpha-hydroxy fatty acid (14-25) (trade name YOFCO-FE-ALF, Japan refine society's system) is carried out methyl-esterified and replace the hexadecanol, use the method identical to make 2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) ester with embodiment 2 with reducing the long-chain branched-chain alcoho of long-chain branched chain fatty acid (12-31) (trade name YOFCO-FE-ALF, Japan refine society's system) gained according to a conventional method.Measuring the transparency liquid that obtains with above-mentioned manufacturing 13Among the R-NMR, as shown in Figure 2, from observe 176.5,170.6,72.1, the signal of 65.3ppm, can confirm to be generated as 2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) ester of alpha-hydroxy fatty acid derivant of the present invention.
The manufacturing of embodiment 5. 2-isobutyl acyloxy Palmic acid Petiolus Trachycarpi esters
Except that the Palmic acid chloride being transformed into the isopropylformic acid. chloride, use the method identical to make with embodiment 1, by 13R-NMR measures the 2-isobutyl acyloxy Palmic acid Petiolus Trachycarpi ester that can confirm to generate alpha-hydroxy fatty acid derivant of the present invention.
The manufacturing of embodiment 6. 2-acetoxyl group Palmic acid Petiolus Trachycarpi esters
Except that the Palmic acid chloride being transformed into acetic acid chloro thing, use with embodiment 1 method mutually and make, by 13R-NMR measures the 2-acetoxyl group Palmic acid Petiolus Trachycarpi ester that can confirm to be generated as alpha-hydroxy fatty acid derivant of the present invention.
The manufacturing of embodiment 7. 2-isoamyl acyloxy dodecoic acids ten diester
Except that 2-hydroxyl tetradecane acid methyl ester being changed into 2-hydroxyl dodecanoic acid methyl ester, 18-methyl eicosanol being changed into lauryl alcohol, and the isopropylformic acid. chloride changed into the isovaleric acid chloride, use the method for making identical to make with embodiment 2, by 13R-NMR measures 2-isoamyl acyloxy dodecoic acid ten diester that can confirm to be generated as alpha-hydroxy fatty acid derivant of the present invention.
The manufacturing of embodiment 8. 2-long-chain branched chain fatty acid (12-31) oxygen base Palmic acid Petiolus Trachycarpi esters
Remove according to a conventional method long-chain branched chain fatty acid (12-31) (trade name: YOFCO-FE-NH, Japan refine society's system) used as chloride and replace beyond the Palmic acid chloride, use the method identical to make with embodiment 1, by 13R-NMR measures 2-long-chain branched chain fatty acid (12-31) the oxygen base Palmic acid Petiolus Trachycarpi ester that can confirm to be generated as alpha-hydroxy fatty acid derivant of the present invention.
Embodiment 9. is by the manufacturing of the alpha-hydroxy fatty acid derivant of down goat
Will from the raw wool of down goat fine, soft fur (pure wool) 1kg through removing roguing hair, sand scholar and outer skin with flowing water washing 24 hours and intensive drying after, under agitation carry out adipose extraction in 2 hours for 2 liters with acetone.Then, filter this extract, obtain the thick extract 35g of cashmere phat fat by under reduced pressure concentrating.(launch solvent: hexane/ethyl acetate=10/1) the refining thick extract of resulting cashmere phat fat, (launch solvent: fraction hexane/ethyl acetate=10/1) obtains the paraffin diester fraction 10.5g of transparent liquid by the Rf value 0.5 in the concentrated TLC analysis with silica gel column chromatography.
Paraffin diester at this fraction 13During R-NMR measures, as shown in Figure 3, from observe 176.5,170.6,72.2, the signal of 65.3ppm, can confirm the mixture of alpha-hydroxy fatty acid derivant of the present invention.
Then, carry out the alkaline hydrolysis and the esterification of the paraffin diester of this fraction according to a conventional method, analyze with gas chromatogram, as alpha-hydroxy fatty acid, with the Alpha-hydroxy Palmic acid as main constituent, its total carbon number is 12-20, except that the side chain product that contains part abnormal shape or anteiso-type, nearly all is the saturated alpha-hydroxy fatty acid of straight chain.On the other hand, as fatty acid, for the satisfied fatty acid of isopropylformic acid. as the side chain of the straight chain of the carbon number 2-6 of main constituent or abnormal shape or anteiso-type.In addition, as alcohol, for being that total carbon number of main constituent is the straight chain of 12-25 or the saturated alcohols of abnormal shape or anteiso-type side chain with 18-methyl eicosanol and 18-methyl nonadecanol.That is to say, thus, can confirm that above-mentioned alpha-hydroxy fatty acid derivant mixture is for meeting the chemical compound of above-mentioned general formula (2).
Fig. 4, Fig. 5 and Fig. 6 illustrate the alpha-hydroxy fatty acid, fatty acid of gained, each gas chromatogram of alcohol.Its mensuration is undertaken by following condition.
Alpha-hydroxy fatty acid, alcohol
Determinator: the system 5890 type II of HEWLETT PACARD society,
Post: DB-1,30m * 0.25mmI.D., 0.25 μ m (J﹠amp; W society system),
Temperature: 100 ℃ (1 minute)-300 ℃ (10 minutes), 5 ℃/minute of programming rates;
Detector: MSD.
Fatty acid
Determinator: the system 5890 type II of HEWLETT PACARD society,
Post: HP-INNOWAX, 30m * 0.25mmI.D., 0.25 μ m (HEWLETTPACARD society system),
Temperature: 2 ℃/minute of 70 ℃ (3 minutes)-100 ℃ of programming rates;
5 ℃/minute of 100 ℃-250 ℃ (5 minutes) programming rates;
Detector: MSD.
Then, the fusing point of the alpha-hydroxy fatty acid derivant of being measured with DSC (differential scanning calorimetry (DSC)) of the present invention is shown in table 1.In addition, 2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi ester for the product of embodiment 1 gained, 2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) ester for being that product, 2-acetoxyl group Palmic acid Petiolus Trachycarpi ester with embodiment 5 gained is usefulness embodiment 6 resulting products with embodiment 4 resulting products, 2-isobutyl acyloxy Palmic acid Petiolus Trachycarpi ester.In addition, as a comparison, use used tripalmitin (Tokyo changes into society's system), cetyl palmitate (Funakoshi society system), ceramide 2 (Cederma society system) and ceramide 3 (Gist-brocades society system) such as cosmetics, topical drug and medicine in the past, its result also one is listed in table 1.But, the final peak value of DSC curve as fusing point.
Table 1
Compound name Fusing point (℃)
2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi ester 52.5
2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) ester 2.0
2-isobutoxy Palmic acid Petiolus Trachycarpi ester 28.3
2-acetoxyl group Palmic acid Petiolus Trachycarpi ester 35.1
Alpha-hydroxy fatty acid derivant by down goat -0.8
Tripalmitin 64.1
Cetin 52.8
Ceramide 2 106.8
Ceramide 3 125.3
As shown in table 1, although alpha-hydroxy fatty acid derivant of the present invention is a saturated compounds, compare fusing point with ceramide also low especially, and also the fusing point than the chemical compound with equal extent molecular weight is low, more approaching with human temperature or skin temperature.Therefore, alpha-hydroxy fatty acid derivant of the present invention is significantly good as the adipose rerum natura of the topical composition that is used for skin or hair grooming compositions etc.
On the other hand, in alpha-hydroxy fatty acid derivant of the present invention, compare the chain length of the fatty acid that the is replaced " R in the described general formula (1) with 2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi ester 2Or the R in the described general formula (2) 5" fusing point of short 2-isobutyl acyloxy Palmic acid Petiolus Trachycarpi ester or 2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) ester, 2-acetoxyl group Palmic acid Petiolus Trachycarpi ester is low especially, more near body temperature or skin temperature.That is, has special excellent characteristic as the oiliness base that is used for topical composition.
Secondly, as safety testing, with the zest of following method research to skin.Using alpha-hydroxy fatty acid derivant that the foregoing description gets to be dissolved in the olive oil and the synthetic sample 1ml of institute is impregnated into contact skin by the concentration of 50wt% tests on the adhesive plaster of usefulness.Then, the wrist medial part sticked 24 hours on 20 testees, judged zest after removing 24 hours that stick.Its result of determination is represented with its positive rate showing obviously and the conduct positive of erythema.It the results are shown in table 2.
Table 2
Test agent Positive rate %
2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi ester 0
2-isobutyl acyloxy tetradecylic acid-(18)-methyl 20 esters 0
2-acetoxyl group stearic acid-(18)-methyl 19 esters 0
2-isobutyl acyloxy long-chain fatty acid (14-25) long-chain branched-chain alcoho (12-31) 0
2-isobutyl acyloxy Palmic acid Petiolus Trachycarpi ester 0
2-acetoxyl group Palmic acid Petiolus Trachycarpi ester 0
2-isoamyl acyloxy dodecoic acid ten diester 0
2-long-chain branched chain fatty acid (12-31) oxygen base Palmic acid Petiolus Trachycarpi ester 0
Alpha-hydroxy fatty acid derivant by down goat 0
As shown in table 2, can confirm that alpha-hydroxy fatty acid derivant of the present invention is to the skin nonirritant.
Application examples 1, ratio example 1 (skin care cream)
Modulate the skin care cream of forming by the one-tenth branch of table 3 according to a conventional method.In addition, be product at application examples 1 used 2-Petiolus Trachycarpi acyloxy Palmic acid Petiolus Trachycarpi ester by embodiment 1 gained.In addition, 1 modulate the skin cream that does not contain alpha-hydroxy fatty acid derivant of the present invention as a comparative example.For women participant 20 people about it leftover bits and pieces position respectively by towards evening 2 times on the one the common practice use the skin cream of 1 all application examples 1 and comparative example 1 to compare benchmark test.In addition, represent that for slickness, wettability, elastic every number the result one of comparison benchmark test is listed in table 3 by answer " skin limbers up ", " skin produces and moistens ", " skin is felt nervous ".
Table 3
Composition name (wt%) application examples 1 comparative example 1
2-palm acyloxy palmitic acid palm ester 15.0-three decanes 5.0 5.0 paraffin 5.0 5.0 cholesterol 0.5 0.5 hydrogenation soybean lecithins 1.0 1.0 glycerin monostearates 1.0 1.0 sorb sugar alcohol acid anhydride monostearates 2.0 2.0 DPGs 5.0 5.0 1,3-BDOs 5.0 5.0 methyl p-hydroxybenzoates 0.1 0.1 refining water all the other all the other that flow
Compare benchmark test result (people)
Slickness 19 1 moistness 18 2 elasticity 18 2
By shown in the table 3, the skin care cream of the application examples 1 of skin composition of the present invention is compared with the comparative example 1 that does not contain alpha-hydroxy fatty acid derivant of the present invention, and all various characteristicses are all good.In addition, application examples 1 no problem on registration property, and can confirm not have the unusual skin defect of zest etc.
Application examples 2. skin care emulsions
Modulate the skin care emulsion of forming by following table 4 with conventional method.In addition, are products of using embodiment 2 gained at application examples 2 used 2-isobutyl acyloxy tetradecylic acid-(18)-methyl 20 esters, and 2-acetoxyl group hard fatty acids-(18)-methyl 19 esters are the products with embodiment 3 gained.The emulsified state of the skin care emulsion of the application examples 2 of skin composition of the present invention is also extremely good.When being used for face or trick etc. and using, be not clamminess, good to skin infiltration, after use, have the excellent functional properties of the skin smoothness of paying, wettability, elastic force.
Table 4
Composition name (wt%) Application examples 2
2-isobutyl acyloxy tetradecylic acid-(18)-methyl 20 esters 3.0
2-acetoxyl group stearic acid-(18)-methyl 19 esters 2.0
Tetradecylic acid octyl group ten diester 2.0
Polyoxyethylene solidifies Oleum Ricini (60E.0) 1.0
Tetradecylic acid 0.5
Glycerol 10.0
Two glycerol 5.0
Maltitol 2.0
Carboxy vinyl polymer 0.2
Potassium hydroxide 0.3
Methyl parahydroxybenzoate 0.1
Ethylenediaminetetraacetic acid potassium 0.1
Purified Water All the other
Application examples 3 (lipstick)
Modulate the lipstick of forming by following table 5 according to a conventional method.In addition, used 2-acetoxyl group Palmic acid Petiolus Trachycarpi ester is the product with embodiment 8 gained for product, 2-long-chain branched chain fatty acid (12-31) oxygen base Palmic acid Petiolus Trachycarpi ester with embodiment 6 gained in application examples 3, is product with embodiment 9 gained by the alpha-hydroxy fatty acid derivant of down goat.The lipstick of the application examples 3 of skin composition of the present invention, its dispersing of pigments well wait registration property good, also are not clamminess after the use, and demonstrate good cosmetic maintenance good functional characteristics.In addition, the thick extract of cashmere phat fat with embodiment 9 replaces comparing the excellent functional properties that also demonstrates some fragrance flavor materials with the lipstick of application examples 3 by the lipstick that the alpha-hydroxy fatty acid derivant of down goat is prepared.
Table 5
Composition name (wt%) Application examples 3
2-acetoxyl group Palmic acid Petiolus Trachycarpi ester 30.0
2-long-chain branched chain fatty acid (12-31) oxygen base Palmic acid Petiolus Trachycarpi ester 20.0
Alpha-hydroxy fat derivant by down goat 10.0
Cera Flava 10.0
Brazil wax 10.0
Octyl dodecanol 5.0
Docosanol 5.0
Pigment 9.8
Spice 0.2
Application examples 4, comparative example 2 (hair rinse agent)
Modulate according to a conventional method by following table 6 and form the hair rinse agent that is constituted.In addition, at used 2-isobutyl acyloxy long-chain (14-25) long-chain branched-chain alcoho (12-31) esters of application examples 4 for the used product of embodiment 4.In addition, modulate the hair rinse agent that does not contain alpha-hydroxy fatty acid derivant of the present invention as a comparative example.20 women participants are used the hair rinse agent of application examples 4 and comparative example 2 in per 3 days by 1 time on the 1st usual way, and carry out the comparing function evaluation test.In addition, the result of comparing function evaluation test also is shown in table 6 with regard to projects such as slickness, wettability, glossinesses in the lump by the number of answering " hair polishes ", " hair is moistening ", " hair is gorgeous " answer.
Table 6
Composition name (wt%) application examples 4 comparative examples 2
The different bytyry LCFA of 2-(14-25) long-chain branched-chain alcoho (12-31) ester 2.0-16 alcohol 3.0 3.0 chlorination stearoyl front three ammonium 1.5 1.5 polyoxyethylene, 16 ethers (10E.0) 1.0 1.0 glycerine 5.0 5.0 methyl p-hydroxybenzoates 0.1 0.1 spices (the plain compound perfume of the meat fragrance of a flower) 0.3 0.3 refining water all the other all the other
Comparing function evaluation test (people)
Slickness 20 0 wettabilities 18 2 glossinesses 19 1
As shown in table 6, to compare with the comparative example that does not contain alpha-hydroxy fatty acid derivant of the present invention with the hair rinse agent of the application examples 4 of hair grooming compositions of the present invention, all features are all good.And application examples 4 is in the problem of registration property, can also confirm not have the unusual skin defect of zest etc.
Application examples 5 (shampoo)
Modulate the shampoo of forming the hair grooming compositions that is constituted according to a conventional method by following table 7.In addition, used 2-isoamyl acyloxy dodecoic acid ten diester are the product with embodiment 7 gained in application examples 5.The shampoo of application examples 5 of the present invention can be confirmed not bubble or problems such as washing performance, and is also lubricious and demonstrate good etc. the functional characteristic of dried slickness, wettability, glossiness when rinsing.
Table 7
Composition name (wt%) Application examples 5
2-isoamyl acyloxy dodecoic acid ten diester 0.1
The dodecoic acid amido propyl betaine -15.0
Cocoanut fatty acid diethanolamide 5.0
Oleum Cocois N-methyltaurine sodium 3.0
Chlorination stearoyl trimethylammonium 0.3
Polyoxyethylene methyl polysiloxane copolymer 0.5
Methyl parahydroxybenzoate 0.2
Citric acid 0.2
Disodiumedetate 0.1
Spice (mandarin orange is a spice) 0.6
Purified Water All the other
By above-mentioned, although new alpha-hydroxy fatty acid derivant of the present invention is but that the saturated compounds fusing point is low, have the non-stimulated grade of skin as the good character of oiliness base, and with these be neccessary composition skin of the present invention with or the registration property and the functional characteristic of hair grooming compositions good.Therefore, the present invention can provide a kind of new skin with above-mentioned premium properties to use or hair grooming compositions.

Claims (5)

1. the topical composition of a used for cosmetic is characterized in that containing more than a kind or 2 kinds of the represented alpha-hydroxy fatty acid derivant of useful general formula (1),
In the formula, R 1Be the alkyl of the straight or branched of carbon number 10-24, R 2Be the alkyl of the straight or branched of carbon number 1-31, R 3Alkyl for the straight or branched of carbon number 11-31.
2. the alpha-hydroxy fatty acid derivant of a used for cosmetic is with the represented chemical compound of general formula (2),
In the formula, R 4Alkyl, R for the straight chain of carbon number 10-20 5Be the straight chain of carbon number 1-5 or alkyl, the R of abnormal shape or anteiso-type side chain 6For carbon number is the straight chain of 11-31 or the alkyl of abnormal shape or anteiso-type side chain.
3. the topical composition of used for cosmetic according to claim 1 is characterized in that containing the described alpha-hydroxy fatty acid derivant of claim 2.
4. according to the topical composition of claim 1 or 3 described used for cosmetic, also contain selected chemical compound at least a chemical compound group of forming by surfactant, polyhydric alcohol, higher alcohol.
5. according to the topical composition of claim 1 or 3 described used for cosmetic, also contain selected chemical compound at least a group of forming by spice, colorant.
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